DE1494443A1 - Process for the production of coatings and films - Google Patents

Description

Process for the production of coatings and films

A number of raw materials or raw material combinations are known for the production of coatings and films. These must meet various requirements with regard to the processing technology and the demands placed on them in practical use. In general, good mechanical Strives for properties such as surface smoothness, hardness, flexibility and solvent resistance. When using in the field of electrical insulation is of course still to come

η adds a good electrical insulating property. Recently, however, the demand for a higher temperature resistance of such products has come to the fore.

It has now been found that a new class of substances, the polyhydantoins, is able to meet such requirements to an outstanding degree. These are hydantoin rings, M, which are linked to one another at their two nitrogen atoms via organic radicals. These substances and their preparation are described below. j

Such products can be prepared, for example, by heating ■ glycine and polyisocyanates and polyisothiocyanates optionally in an organic solvent at temperatures between 80 and 500 ⁰ C.

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Suitable glycine derivatives are compounds of the general formula _D

Ar-f-NH-C-CORo) _v . ^R 1

where Ar is an aromatic radical, R, j is hydrogen or alkyl, R _{2 is} the hydroxyl group, an araino group, an alkylamino, dialkylamino, alkoxy or aroxy group and χ is an integer between 2 and 4. The requirement for glycine derivatives to be used according to the invention is therefore that they contain the remainder

NH - C - COR «) ' ι ^

must contain at least twice in the molecule.

The aromatic radicals Ar are in particular those of benzene, azobenzene, naphthalene, anthracene, diphenyl, triphenylmethane, Diphenylmethane and diphenylether derived radicals. These Residues can also be substituted one or more times, for example by alkyl (methyl), halogen (chlorine), nitro, Alkoxy (methoxy), dialkylamino (dimethylamine), acyl (acetyl), Carbalkoxy (carbomethoxy or ethoxy) and Cyano groups.

They are preferably carried out once or twice Methyl and / or chlorine-substituted benzene, naphthalene, diphenylmethane or diphenyl ether derivatives.

The preparation of the glycine derivatives to be used as starting materials is known in principle and can be carried out, for example, by direct reaction of aromatic polyamines with haloacetic acid or its derivatives or by condensation with hydrocyanic acid and aldehydes or ketones with subsequent conversion of the nitrile group into e.g. carboxylic acid, ester or Amide.

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The reaction with haloacetic acid or its derivatives takes place in organic solvents, e.g. in ethanol, methanol, Acetone, benzene, or "in an aqueous medium with use of acid scavengers, such as tert. Amines (e.g. pyridine, triethylamine), excess starting amine, soda, potash, Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, Potassium hydroxide, calcium oxide, calcium carbonate.

The haloacetic acid or its derivatives include, for example, chloroacetic acid, Chloroacetamide, Ν, Ν-dialkyl chloroacetamide (dimethyl, Diethyl, dibutyl), chloroacetic acid ester (methyl, ethyl, phenyl), ec-chloropropionic acid ester or Λ-chloropropionic acid etc. are possible.

Another method is the condensation of the aryl polyamines with cyanides (NaCN, KCN) and oxo compounds (formaldehyde, acetone, acetophenone) with the addition of acids; the received Nitriles can then be saponified in a known manner to give carboxylic acids or converted directly into esters with alcohol / HCl. Further Processes consist in the conversion of already prepared glycine derivatives, e.g. in an esterification of the free Acids or aminolysis of esters.

Suitable aromatic polyamines are compounds with at least two aromatically bound amino groups, which, however, should not be arranged in the o- or peri-position. The amines can also be substituted as desired. Examples of such aromatic polyamines are: m- and p-phenylenediamine, 2,4-, 2,5- and 2,6-tolylenediamine, diisopropylbenzene-diamine, 1,3,5-triaminobenzene, 2,4,6- Triaminotoluene, 4,4 ^l -diamino-azobenzene, 2,4,6-triaminoethylbenzene, • 1,3,5-triisopropylbenzene-diamine, 2-chloro-l, 4-, 2 , 5-chier-1,4-, 2,6-dichloro-1,4-phenylene-, 2,6-diamino- and 4,6-piamino-5-methyl-1,3-diethylbenzene, 1,3-, 1,4-, 1,5- , 1,6-, 1,7-, 2,4-, 2,5-, 2,7- and 2,8-diaminonaphthalene, 1,4-diaminoanthraquinone, 1,5-diaminoanthrarhinone, 4.4 ^f -, 2,4 ^f -diamino-diphenylthioether, 4 _r 4 ^f -diamino-diphenyl disulfide, 4,4'-diamino-diphenyl, 4,4'-

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Diamino-3,3 * - or -2,2 ^fl -dichlorodiphenyl, 4,4'-diamino-3,3'-dialkoxy-diphenyl, 4,4'-diamino-3,5'-diraethyl-diphenyl, 4 , 4'-diamino-diphenyl methane, 2,2'-bis-p-aminophenyl-propane, 4,4'-diamino-stilbene, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenyl ether, 4,4 ' -Diamino-diphenylsulfone, 4,4 ', 4 "-Triamino-triphenylmethane, diamino-carbazole, 2,4-diamino-6-phenyltriazine- (1,3,5). Furthermore also higher molecular weight compounds with several amino groups in aromatic bond, for example aniline-formaldehyde resins.

Suitable polyiso (thio) cyanates are, for example, aliphatic, cycloaliphatic or aromatic compounds with at least two NCO or NCS groups in the molecule. Examples of such polyisocyanates are: Polymethylene diisocyanates OCN- (CH ₂ ) _n -NCO with η = 4 to 8, optionally alkyl-substituted benzene diisocyanates such as m- and p-phenylene diisocyanates, toluene-2,4- and 2,6-diisocyanate, Ethylbenzene diisocyanate, di- and triisopropylbenzene diisocyanate, chloro-p-phenylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, ester isocyanates such as triisocyanato-arylphosphorus (thio) ester or glycoll-p-isocyanatophenyl ester. Partially polymerized isocyanates with isocyanurate rings and free NCO groups are also possible.

The polyisocyanates used can also be in the form of their derivatives can be used. Here come z. B. the reaction products with phenols, alcohols, amines, ammonia, bisulfite, HCl, etc. are possible. Examples include phenol, cresols, xylenol, ethanol, methanol, propanol, isopropanol, Ammonia, methylamine, ethanolamine, dimethylamine, Aniline, Diphenylamine Furthermore, higher molecular • adducts, e.g. of polyisocyanates with polyalcohols such as ethylene glycol, Propylene glycol, trimethylolalkane or glycerin can be used.

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Instead of the listed polyisocyanates, the thio analogs can analogously can be used.

The manufacturing process is generally carried out in such a way that that the two starting components are heated in an organic solvent for a long time, the resulting polymer remains in solution. It can then be isolated by distilling off the solvent. The quantities of the starting substances can be chosen so that per mole of NH group of the glycine derivative 0.5 to 10 moles of isocyanate or isothiocyanate groups are available, preferably 1 to 3 moles of isocyanate or isothiocyanate are used. For the procedure Suitable solvents are compounds which are inert towards NCO groups, e.g. aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, Esters and ketones.

N-alkyl pyrrolidones, dimethyl sulfoxide, Phenol, cresol and dimethylformamio .. When using iso (thio) cyanate derivatives other solvents, for example alcohols, phenols, can also be used. But it is also possible to implement the components in substance.

The reaction times are between 30 minutes and 20 hours, but in special cases can also be higher or lower. The reaction temperatures are chosen ^{between 80 and 500 °} C., depending on the starting material. Is preferably carried out at 100 to 35O ⁰ C, the best results are obtained in the range 140-280 ⁰ C.

These condensation reactions can be achieved through the use of catalysts, e.g. metal alcoholates, tert. Amines, .accelerated.

In addition to the polymerization, the two condensation takes place Reaction partners a ring closure reaction to the hydantoin ring, which are illustrated by the following reaction scheme

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^ \ - NH - CH ₂ -COR ₂ + -NCX. > ~~ \ -N

Il

Such polymers change into hard, infusible products when heated to higher temperatures. So you can get through Application of solutions of these substances in suitable solvents or solvent mixtures on heat-resistant substrates such as metals, ceramics, glass or asbestos fans or the fabrics made from it or on other correspondingly temperature-resistant plastics by baking at elevated temperatures Temperatures produce coatings that have excellent α flexibility and surface hardness as well as excellent Abrasion resistance and resistance to all common solvents such as alcohols, aromatic and aliphatic Hydrocarbons as well as esters, ethers and ketones and also gecen Own water.

Polycondensates containing hydantoin or thiohydantoin rings, in which the hydantoin rings, via their nitrogen atoms, with divalent organic radicals such as alkylene radicals with 4 to 10 carbon atoms, phenylene radicals, toluene radicals _; Diphenylene residues and diphenylene ether residues are linked to one another.

P For the preparation of the solutions of these polycondensation products preference is given to using solvents such as dialkylamides, e.g. dimethylformamide or diethylacetamide, also N-methylpyrrolidone, Dimethyl sulfoxide or cresols.

More generally represents one coatings of the hydantoin bzwi Thiohydantoinringe containing condensates so forth by dissolving these materials in a suitable solvent, is applied to a substrate and cured by heating at temperatures between 150 and 500 ⁰ C. These solutions can contain about 10 to 50 % solids.

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These good and desired properties are largely retained or can still be used in this or that direction vary when using other known polymeric substances, e.g. polyesters, polyamides, polyurethanes, polyolefins, polyacetals, Polyepoxides, polyimides, polyamide-imides, polyimino polyesters, polyimide isocyanates are also used. The quantity ratio Such additives are largely based on the required properties of the end product and can be in the ratio of 10: 90 to 90: 10 fluctuate. Preferably one will be in proportion Mix 50:50. Such materials can be mixed with the polyhydantoins, but can also be polymerized into them will.

A special embodiment consists in the co-use of hydroxyl group-containing polyesters using excess Amounts of iso (thio) c3 ^ anate component, which leads to a combination of (thio) hydantoin and urethane formation. For this purpose, e.g. mixtures of the polyhydroxyl compound, polyisο (thio) cyanate (derivative) and polyglycine derivative, possibly after precondensation of two of these components, in a simultaneous final operation transferred into the plastic.

As polyesters containing hydroxyl groups, the known types are used, such as those obtained from polycarboxylic acids, e.g. succinic, Adipic, sebacic, phthalic, isophthalic, terephthalic, oleic acid and polyalcohols, e.g. glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerine, trimethylolpropane, Pentaerythritol, can be obtained in a conventional manner.

Generally it has been shown that when applying several Layers on top of one another have excellent adhesion to one another. One can do this advantageously for the production Take advantage of laminates, for example by using fiberglass sheets or fabric painted with such a solution and usually after drying at low temperatures

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■ · superimposed in several layers and the same under Application of pressure and heat cures. In this way, laminates with good mechanical properties are obtained, such as Impact resistance, flexural strength and high elasticity.

Likewise, mica platelets with such Solution are painted, stick together and thus result in a valuable material, for example in the electrical industry is used.

"* The excellent electrical insulation properties also allow the advantageous use of solutions of such products in the electrical insulation field. An electrical winding is immersed in such a solution and the coil soaked in this way is burned ^{in the oven at approx. 150 °} C. The winding is then firmly baked and provides good mechanical protection at higher temperatures possibly occurring centrifugal, forces. this should dip conveniently a temperature of about 50 ⁰ C have, because the viscosity of the solution then is low enough to complete penetration of festgewicfcelten Hard but tough films have proven to be suitable for this application, such as those resulting from the reaction of glycine derivatives of 4,4'-diaminodiphenyl methane with 2,4 -Toluylene diisocyanate; measured according to VDE 0360, the caking number of such a varnish is b at 155 ⁰ C 3.2.

The same paint solution can also be used as a top coat over already Soaked and baked coils are used to make the • To give the winding further mechanical protection.

For the production of fabric impregnations, such as those used as bandage material or as insulating tubes, a flexible material is primarily desired. One such

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. can be, through the use of cycloaliphatic or aliphatic · tables Diisocyanateh received, which a longer and thus have more flexible carbon chains. One uses for this The purpose is preferably reaction products of the glycine derivative of 4,4 * -diajnino-diphenyl-ether with hexamethylene-diisocyanate-1,6. But there are also other, similarly structured diisocyanates, such as hexamethylene di-th'io-isocyanate or 1,4-diisocyanatodibutyl ether suitable.

A key area of application for these polyhydantoins is as wire enamel. Here the requirements with regard to the process engineering as well as with regard to the properties of the electrical conductor coated in this way are particularly diverse. The coating solution must be adapted to the various types of application machines. The wire usually passes through a paint bath, behind which the excess paint is then wiped off by a special wiper system. This can consist of two felts pressed together through which the wire is passed. For this process, a varnish of relatively low viscosity is required, which is achieved by selecting suitable solvents with a solids content of up to about 40 %, preferably up to 20-30 % . The diameter of the wire to be coated also plays a role here. The increases in the diameter of the wire that can be achieved by painting are specified in DIN regulations 46 and 46 435. A more viscous solution or a solution with a higher solids content is usually wiped off by means of metallic wiper nozzles.

The wire then passes through a stoving furnace in which " The effect of heat evaporates the solvent and the curing of the paint film is effected. This process is repeated several times until the required layer thickness is achieved. Most of time 6 to 8 passages are required for this.

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In a painting attempt with a wire 0.7 mm in diameter, the furnace length is, for example, 4.2 m and the temperature 40O ⁰ C. The speed at which the wire is drawn through the furnace is 6 m / min. This speed can be increased to 10 m / min without the properties of the enamelled wire obtained dropping. A 6-fold application of lacquer results in an increase in diameter d ₂ (diameter of the lacquered wire) minus d ^ (diameter of the bare copper wire) of 64 μm, ie the lacquer film thickness is 32 μm. The enamelled wire obtained in this way has excellent abrasion resistance and shows particularly good behavior when exposed to heat shock. It also has high abrasion resistance, good dielectric strength and high paint film hardness.

For testing the abrasion resistance according to the NEMA method For example, between 100 and 150 double strokes have been achieved. The applied weight varied according to the thickness of the paint film between 550 and 600 g.

If the wire is wrapped around a mandrel of its own diameter, i.e. by 0.7 mm, and the wire coil obtained in this way is placed in a heating cabinet that ^{is preheated to 260 °} C., no cracks or breaks in the paint film can be found after 60 minutes ( Heat shock according to DIN 46453).

When determining the softening temperature according to DIN 46453, the coated wire is loaded by a steel pin which crosses at an angle of 90 ° and on which the weight of 1 kg rests. Intermediate j the steel pin and the copper is a voltage of 150 V. This device is located in an oven whose temperature of 50 ° C / hour is increased. "In the temperature range in which the film due to its thermoplasticity softened f- expressed the steel pin through the paint film.

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As a result of the direct contact between the steel pin and the copper wire, an acoustic signal is triggered, which indicates the end point of the test. In all within the above operating range (400 ° C, 6 his IO m / min.) The baked coating wires of the furnace could be heated to its final temperature of 33O ⁰ C "without the coating film was pressed by the steel pin. ·

The breakdown voltage, measured on twisted wire samples, (DIN 46 453) is between θ and 9 kV.

The hardness of the paint film (DIN 46 453) is 5 H. This value is retained even if the enamelled wire is exposed to _

Is exposed in ethanol at 50 ^{0 C for 30 minutes.} ™

Furthermore, the coated wire does not show any hairline cracks when it is bent under water. To test for bending the wire in a 0, ^59% £ saline solution to a withers of 10 mm diameter, and places a DC voltage of 100 V to the water bath and the copper conductor to. In the event of hairline cracks, a current would flow and an interposed control lamp would light up.

The coating solutions of the invention generally contain suitable solvents or mixtures, wherein experience a certain proportion can be mitverwandt of non-solvents in accordance with., Λ as the solvent can be for example, aromatic hydrocarbon e, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, esters and ketones use. Particularly suitable are N-alkylpyrrodon, dimethylsulforide, dimethylsulphone, dimethylformamide, diethylacetamide, phenol and cresol or mixtures thereof.

The solids content of the solutions can be within wide limits vary and depends both on the type of binder and its dissolving behavior as well as on the intended one How to use, as a guide you can probably

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think of solutions with a solids content of 10 to 60 %. For example, in the case of lacquers for lacquering wires on the normally used lacquering machines, a solids content of around 10 to 45 % is used, depending on the type of application and wire thickness. Impregnating varnishes for impregnating coils, on the other hand, usually have a solids content of around 35 to 50 %.

It was further found that the hardening reaction goes through. Addition of suitable catalysts can be accelerated, ie the reaction time is shortened or the stoving temperature is lowered at the same time. This is important for complete curing on particularly fast-running wire enamelling machines. Such catalysts are: Organic metal compounds such as titanium, lead, copper, iron or alkaline earths. Furthermore, amine and ammonium compounds, in particular quaternary salts, such as, for example, tetramethylammonium acetate, tetramethylammonium terephthalate and choline octoate, can also be used. As a rule, 0: 0.5 to 3.0% of these catalysts, based on the solids content of the paint, are used. Although higher additions are possible, but do not produce noticeable benefits more.

Example 1:.

CH3 0

42 parts by weight CH-CO-CH ₉ -CH,

/ t \ »2 3

n = N / A

CH ^ -CH ₀ OC-CH
3 2 η ι

are dissolved in 50 parts by weight of dimethylformamide and mixed with 20 parts by weight of 2,4-tolylene diisocyanate while stirring and slowly heating. After the addition is complete, the mixture is heated to a gentle boil for a further 15 minutes. The mixture is cooled to about 5O ⁰ C, and added a solution of 20 parts by weight of a poly

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esters with 5.5 % OH and an acid number of 4.1 dissolved in 40 parts by weight of kres oil. Such a polyester is obtained by esterifying 2 pounds of adipic acid, 2 moles of terephthalic acid, 3 moles of trimethylolpropane and 2 moles of ethylene glycol. The lacquer solution obtained in this way is further diluted with 33 parts by weight of methyl or ethyl glycol acetate and applied to a deep-drawn sheet by dipping. After flashing off the Hauptrnenge the solvent at room temperature will be in the oven for 1/2 hour, baked i 180 ⁰ C. A glossy, heat-resistant elastic film of good surface hardness is obtained.

Example 2;

370 parts by weight are dissolved

in 400 parts by weight of dimethylformamide and adds 180 parts by weight of hexamethylene-1,6-diisocyanate and 100 parts by weight of a polyester with about 5% OH and an acid number of 1.2 dissolved in 300 parts by weight of ethylglycol acetate. The polyester is obtained by esterifying 3 moles of adipic acid, 1 mole of trimethylolpropane and 3 moles of butylene glycol. This mixture is heated for 4 hours to about 13O ⁰ C and then cooled. It is further diluted with 1000 parts by weight of a solvent mixture | consisting of 3 parts by weight of cresol, 4 parts by weight of methyl isobutyl ketone and 3 parts by weight of methyl glycol acetate.

This resist solution is coated on a suitable therefor apparatus in known manner, a glass fiber fabric, and then to 2 m in a tunnel kiln of 8 m of shaft length at a temperature of 29o ⁰ C and a pulling rate of 1 cured per minute. The result is a flexible lacquer fabric with good electrical properties which are retained even after prolonged heat aging.

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Example 3:

370 parts by weight of ri, IJ ^l-bis-l-4,4 carbäthoxymethyl -diaiiiinodiphenylmethan be at -15O ° C in 1000 parts by weight of cresol, where ^f previously 25Θ parts by weight of 4,4 -DiisocyanatodlphenyInethan were added, registered and 6 hours at 180 ⁰ C. condensed. The resulting coating solution has a viscosity of 25000 .cp at 25 ⁰ C. For this purpose, to add further 900 parts by weight of a mixture of 570 parts by weight of xylene and 330 parts by weight of cresol. With this paint, a copper wire of 0.7 mm diameter in the conventional manner is painted on a Lackier "machine in Figure 6 by trains. The enamelled wire obtained has good abrasion resistance at a softening temperature of over 30O ⁰ C.

Example 4; .

372 parts by weight of N.N'-bis-carbäthoxymethyl - ^^ '- diphenyl ether are added at 150 ° C in 1300 parts by weight of cresol, to which 236 ^{parts by weight of 4.4 l} -diisocyanato-diphenyl ether have already been added, and 6 hours at 180 ° C condensed. After cooling, 600 parts by weight of xylene are added and this lacquer solution is used to lacquer copper wires, as described in Example 3. The Kirpfer ^ irafat obtained shows good heat shock resistance, a softening point of over 330 ° C. and excellent abrasion resistance.

Example 5;

To 660 parts by weight of the solution prepared according to Example 4, the cresolic solution of 34.6 parts by weight of a. Epoxy compound with an epoxy equivalent weight of 1700 to 2000, produced by reacting epichlorohydrin and diphenylolpropane in 305 parts by weight of cresol, added.

The enameled wires made with this enamel solution are very elastic.
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Basically, epoxy resins with epoxy equivalent weights can be used combine between 400 and 4000. Also those based on aromatic amines and epichlorohydrin, as well as those of the cycloaliphatic epoxy compounds are suitable, owing to the large number of conceivable combinations and mixing ratios In turn, extensive modification of the flexibility is possible.

Example 6;

372 parts by weight of N.N'-bis-carbäthpxymethyl ^^ '- diphenyl ether are dissolved in 1000 parts by weight of cresol. A solution of 846 parts by weight of a blocked isocyanate of the following composition is added to this:

in 1500 parts by weight of cresol / xylene 1: 1. The mixture is heated to 170 to 180 ° C. for 6 hours and, after cooling, a further solution of 460 g of a polyester, dissolved in 1250 parts by weight of cresol, is added. The polyester with 5 % OH is by condensation of 8 moles of dimethyl terephthalate with. 6 moles of ethylene glycol, 1 mole of trimethylolpropane and 2 moles of glycerol were obtained. Now is further diluted with 1000 parts by weight of xylene while stirring and a copper wire from with this lacquer solution in the usual way

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.0.3 mn diameter painted. This gives a good heat-resistant enameled wire of excellent heat shock resistance up to about 25O ⁰ C, a good abrasion resistance, high solvent resistance and high softening temperature.

Example 7:

To 606 parts by weight of the solution prepared according to Example 4, 20 parts by weight of a polyester containing imide groups, prepared from 200 parts by weight of ethylene glycol, 92 parts by weight of glycerol, 75 parts by weight of 3-amino-1-propanol, 109 parts by weight of pyromellitic dianhydride and 432 parts by weight of W terephthalic acid-bis- glykolester with the addition of 0.4 parts by weight of PbO and 2.1 parts by weight Zn octoate at 200 ⁰ C in vacuo (555 parts by weight of the product, the strength in 33.5% cresol solution having a viscosity of CP ₂₅ = 4950) dissolved in 372 parts by weight of cresol , admitted.

A copper wire with a diameter of 0.5 mm is coated in a known manner with the paint solution thus produced. The enamelled wire obtained has good flexibility, heat shock resistance, high softening temperature and dielectric strength. The long-term temperature resistance is excellent, that the measured values remain good even after heat storage J ^ j over a long "period received.

Example 8;

500 parts by weight of the paint solution prepared according to Example 5 are mixed with 250 parts by weight of the solution of a condensate, which contains imide and amide groups and does so in the following manner was produced:

A mixture of 40 parts by weight of 4,4'-diaminodiphenyl ether and 38.4 parts by weight of trimellitic anhydride is heated to 150-205 ^° C. for 6 hours in a closed pressure vessel

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heated. After cooling, the reaction vessel is opened and then heated again while passing nitrogen under normal pressure for 30 minutes to about 22O ⁰ C. The condensation product obtained is dissolved in 285 parts by weight of a mixture of dimethyl sulfoxide and diethylacetamide in a ratio of 1: 1.

A copper wire with a diameter of 0.5 mm lacquered with this combination is very heat-resistant and has high heat shock and abrasion resistance in addition to good flexibility and a high softening temperature. . ^

Example 9; -

74 parts by weight a purified by recrystallization from ethyl acetate and ethanol N, N'-bis-ethoxycarbonylmethyl-4,4'-diaminodiphenylmethane with a melting point of 88 ° was dissolved in 290 wt. least. Cresol go. Dissolves and at 40 ° in 2 portions a total of 50 parts by weight. 4, .4'-Diisocyanato-diphenylmethane added. It is then heated to 200 ° for a further 6 hours. The solution obtained (S94 parts by weight) has a viscosity of 2200 cP ₂₅ after dilution with the same amount of cresol.

The solution obtained can also be mixed with acetone, f [ Ethyl acetate or glycol monomethyl ether acetate are precipitated. This gives about 105 parts by weight. of a solid product, which can be resolved again to an analogue cresol solution.

By diluting the above 30% cresolic solution with a solvent mixture of cresol-xylene in a ratio of 1: to a solids content of 20 % , a solution suitable for painting copper wires is obtained. Enamelled wires as described in Example 4 give enamelled wires of excellent flexibility, resistance to heat shock and solvents, a high softening point and excellent abrasion resistance.

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Example 10;

79 »6 parts by weight. N.N'-Bis-methoxycarbonyl-dimethyl-methyl) -4.4 ^f -diamino-diphenylmethane (melting point 117 °) in 302 parts by weight. Cresol are at 60 ° with 50 wt. Tin. 4,4'-Diisocyanatodiphenylmethane was added and the mixture was heated to 200 ° for 10 hours. The solution obtained has a viscosity of 650 cP _oc - after dilution with the same amount of cresol.

To 500 g of the 30% solution thus obtained is after The solution of 150 g of the terephthalic acid polyester prepared according to Example 7 in 550 g of cresol is added to cool.

• z.

1.5 g of polymeric butyl titanate are in approx; 20 cnr cresol dissolved and briefly heated. The cooled solution is added to the lacquer solution and a copper wire is lacquered with this mixture. In addition to good heat shock resistance and a high softening point of the magnet wire produced has excellent windability, the day 14 and after aging at 200 ⁰ C is still present.

Example 11:

61.5 parts by weight. N, N'-bis (methoxycarbonyl-dimethyl-methyl) -mphenylenediamine are available in 261 parts by weight. Dissolved cresol and at 40 ° 50 parts by weight. 4,4'-diisocyanatodiphenylmethane added. It is brought to 200 ° in 3 hours and held at 200 ° for 6 hours. A solution of the polyhydantoin is obtained which, after dilution with equal proportions of cresol, has a viscosity of 185 ^cP and has the typical absorption bands of a hydantoin in the IR spectrum.

At 500 parts by weight. (the 30 # solution in cresol) are added 50 parts by weight. of a polyester made from adipic acid, terephthalic acid, trimethylolpropane and ethylene glycol - prepared according to Example 3 - in 100 wt. Cresol. It is diluted with 150 wt. Tin. Ethyl glycol acetate. The lacquer solution obtained in this way is applied to a metal sheet and, after flashing off, Te A 9346

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STDE; 1 ^1/2. Burned in at 180 - ROO ⁰ C. The heat-resistant film obtained has an excellent surface hardness .

Example 12; '

80.8 parts by weight. NJI'-Bis-CmethoxycaVbonyl-dimethyl-methyl) -4.4 ^l -diaminQdiphenylmethane, 37 parts by weight. Ν, Ν'-bis-ethoxycarbonyl- ^ A'-dia ^ inodiphenylraethane and 275 parts by weight. Cresol are at 50 ° with 50 parts by weight. 4,4 '-Diisocyanatodiphenyl- methane added, in 5 hrs. Brought to 200 ° and held for 3 hrs. At 200 °. The in an amount of 379 wt. TIn. solution obtained shows the IR spectrum of the typical hydantoin * bands and has a viscosity of 419 cps at ₂ 5 after dilution with the same amount cresol.

This lacquer solution, diluted with cresol to a solids content of approx. 20% , used to lacquer copper wires, produces enamelled wires of very good heat shock resistance, great hardness and a softening point of over 330 ° C.

example 13:

67.6 parts by weight. N, N'-bis-ethoxycarbonyl-methyl-4,4'-diaminodiphenylmethane and 10.9 parts by weight. of the analogously prepared N, N ', N "-tris- (ethoxycarbonylmethyl) -4,4', 4" -triamino-triphenylmethane are analogous to Example 12 with 50 wt. tin. 4,4'-Diisocyanatodiphenylmethän implemented.

The solution thus obtained is diluted to a solids content .of 22% with cresol and then in the already described mold for coating copper wire of 0.7 mm diameter used. This results in enamelled wires of high surface hardness and high softening point of about 33O ⁰ C.

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Example 14;

In an example analogous to Example 13, 9.15 weight percentages are used as the trifunctional component. N, N ¹ , N "-Tris-ethoxycarbonylmethyl-2,4,4'-triaminotriphenyl (melting point 102 °) are used.

After dilution to a solids content of 22 % with cresol, a Cu wire 0.7 mm in diameter is painted. The enameled wire obtained has a hardness of 5 H. Even after exposure to ethanol at 50 ⁰ C for half an hour does not decrease this value. In addition to excellent abrasion resistance, a high softening temperature was found.

Example 15:

74 parts by weight N ^ '- bis-ethoxycarbonylmethyl ^^' - diaminodiphenylmethane are in 310 parts by weight. Cresol at 80 ° initially with 13.6 wt. Tin. an isocyanurate triisocyanatephenyl releaser implemented that of 2,4-tolylene diisocyanate by 50% polymerization of the NCO group and subsequent Treated with phenol with an MCO content of 12.4% became. It is held at 80 ° for 1 hour, then heated briefly to 160 ° / 12 Torr to remove the ethanol formed and cooled to 50 ° and still sets 45 parts by weight. 4,4'-diisocyanatodiphenyl methane to. The solution is converted into the desired final state by heating at 200 ° for 6 hours.

The solution obtained is diluted to a solids content of 22% with cresol. Enamelled wire coated with this material has good heat shock resistance, great hardness and resistance to solvents. The softening temperature is above 33O ⁰ C and the abrasion values around 100 double.

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Example 16; .

74 weight tie. N, N'-bis (ethoxycarbonylmethyl) -4,4'-diaminodiphenylmethane and 260 parts by weight. Cresol earths at 50 ° with 37.5 wt. Tin. 4,4'-Diisocyanato-diphenylmethane was added and the mixture was heated to 200 ° for 2 hours. The solution obtained has a viscosity of 118 cPgc.

At 238 parts by weight. the solution obtained is given the cooled solution of 5 »2 wt. tin. of a triisocyanate stabilized with cresol and prepared by trimerizing toluene diisocyanate in 40 wt. tin. Cresol. With another 142 parts by weight of tin .. cresol is then further diluted. An article prepared by using this resist solution enamelled copper wire has excellent abrasion resistance and solvent resistance, and has a softening point of about 33O ⁰ C.

Example 17:

74 wt . N ^ '- bis-ethoxycarbonylmethyl ^ A'-diaminodiphenylmethane and 145 parts by weight. Glycol monomethyl ether acetate are heated to 80 ° and 50 parts by weight. Diphenylmethane-4,4 ^! -diisocyanate registered. The mixture is heated to reflux for 6 hours and 260 parts by weight are obtained. a homogeneous solution.

One according to VDE 0360, p. 21, shown wire spool is immersed in the paint solution. After removing it from the soaking bath, the excess lacquer solution is allowed to drip off. Most of the solvents evaporate during this time. Starting at 120 ⁰ C is then baked in a heating furnace and the temperature is raised to 160 ° C for 2 hours. The coil remains at this temperature for an additional 8 hours. A second dip is then carried out and baked in using the same baking process.

According to VDE 0360, p. 21, the impregnated coil produced in this way has a caking number of 3.2 at 155 ° C.

909841 / U22

Example 18:

'a) 68.4 parts by weight of an N, N'-bis (methoxycarbonylmethyl) -4,4 · -diaminodiphenylmethane obtained by condensation of 4,4'-diamino-diphenylmethane with formaldehyde / hydrocyanic acid and subsequent acidic saponification with methanol mp. 118-119 ⁰ C (from acetone) 1 part by weight Endoäthylenpiperazin are diluted with 290 parts by weight of cresol, was added and then 50 parts by weight of 4,4 ^l diisocyanato-diphenylmethane at 25 ° C was added. The mixture is left to stand for 6 days at room temperature and then heated to 200 ^° C. for 6 hours. 396 parts by weight of product are obtained which, after dilution with the same amount of cresol, have a viscosity of CP ₂₅ = 3220. .

b) Instead of 1 part by weight of endoethylene piperazine, 2 parts by weight of dimethylbenzylamine, 1 part by weight, were analogously Triethylamine or 2 parts by weight of N-methylmorpholine are used and obtained practically the same viscosities.

A solution prepared according to Example 18 a) or according to Example 9 is given with a pouring device in a predetermined Thickness on a heat-resistant base, which can e.g. consist of metal, glass or similar and from which the finished Foil can lift off easily, applied. By warming up

«150 to 20O ⁰ C the solvent is evaporated and the - finished film is peeled from the base.

The film produced in this way has good mechanical properties and high thermal stability with a melting point above 350 ° C.

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Example 19:

80 parts by weight of one prepared according to Example 14 cresolic solution with 20 parts by weight of toluene diluted and then with 60 - 120 parts by weight of a suspension consisting of 1 part aluminum powder (pasty) and 1 part cresol / toluene 1: 1 and stirred with a glass rod. Final addition of 30-15 parts by weight cresol / toluene 1: 1.

By spraying painted sheet for 45 minutes at 250 ⁰ C are burned with prior compliance with the relevant Ablüftezeiten. The ™ coated with the product obtained

and stoved sheets show after one hour of heating * 'to 400 ⁰ C and subsequent exposure to a SO _? Atmosphere (Kesternich test) a good, paint-technical property profile.

Example 20:

a) 79.6 parts by weight. N.N'-Bis-Cmethoxycarbonyl-dimethyl-methyl) -4,4'-diaminodiphenylmethane are available in 100 wt. andest. technical cresol dissolved, 0.2 parts by weight. Endoäthylenpiperazin added and then a solution of 50 wt .- TIn at room temperature. 4,4'-Diisocyanato-diphenylmethane was added dropwise. On the next day, 200 parts by weight. techn. The cresol mixture was added and the mixture was heated to 200 ° under nitrogen for 10 hours, the xylene added being distilled off. Approx. Parts by weight are obtained. a cresolic polyhydantoin solution which, after dilution with equal proportions of cresol, has a viscosity of approx. 10,000 cP _oc .

b) 300 parts by weight. above solution with 100 wt. TIn. a polyester made from terephthalic acid, glycol and glycerine (6 % OH) and 10 wt. tin. that described in Example 19

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■ U9AA43

Isocyanate releasers mixed. This mixture is in the usually applied to copper wires. The properties given in Example 16 are obtained at a softening temperature by 300 °.

c) The solution obtained according to b) was stirred at 130 ° for 2 hours before baking. The processing takes place in analogous procedure and provides a coating with the same properties with a uniform course.

Example 21:

^ 75 parts by weight of a polyvinyl formal with an OH content of 5 to 6 % are dissolved in a 1: 1 solvent mixture of cresol / xylene. 22.5 parts by weight of the 50% strength solution of an adduct of 1 mole of trimethylolpropane, 3 moles of tolylene diisocyanate and 3 moles of phenol in methyl glycol acetate are added to this solution, and the mixture is heated to 130 ° to 140 ° C. for 60 minutes. Thereafter, 75 parts by weight of a 60% strength butanolic solution of a cresol formaldehyde resin and 86 parts by weight of a 30% strength cresolic polyhydantoin solution prepared according to Example 3 are added. A 1: 1 solvent mixture of cresol / xylene is used to dilute to processing consistency. An article prepared with this coating solution by the customary processes enameled wire is up to 260 ⁰ C heat shock

K fixed. The softening temperature depends on the degree of stoving between 250 and 320 ° C.

When using catalysts such as phenol sodium, Sodium nitrophenol, nitrophenol, iron hemiporphyrazine, the take-off speed can be increased even further when enamelling the wire.

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Example 22:

a) With the paint solution prepared according to Example 4 is a common enamelled terephthalate wire according to DIN 46435 (L) For a copper diameter of 0.7 mm, lacquered to double lacquer thickness (2 L). The newly applied polyhydantoin paint film adheres firmly to the original paintwork.

b) A copper wire with a diameter of 1 mm is drawn with a lacquer based on polyvinyl formal / phenolic resin by means of 4 passages to an increase in diameter of 1.030 mm and then lacquered with a lacquer solution prepared according to example 4 by means of further passages to 1.045 mn. The two different paint systems, adhere firmly to each other. The polyhydric film provides improved flexibility after aging and increased thermal compressive strength.

Example 23:

21 parts by weight

CH ₃

f ^ f-HH-CO-NH ₂

v:

NH-CO-NH ₂

and 22.5 parts by weight of NjN'-bis-carboxymethyl-p-phenylenediamine are each dissolved in 50 parts by weight of cresol, the Solutions mixed and heated to 180 ° C for 3 hours. After cooling, a further 70 parts by weight of cresol and 0.5 parts by weight are added Ethanolamine too. A copper sheet is coated with this lacquer solution by dipping. After burning in 1/2 hour at 180 to 200 ° C, a temperature-resistant paint film with good abrasion resistance is obtained.

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909841 / U22.

■ Example 24:.

Dissolve 105 parts by weight of 1,5-diisocyanato-naphthalene and 157 parts by weight of N in each 250 parts by weight of cresol, N'-Biscarboxymethyl-4,4'-diaminodiphenylmethane, unites the two 'solution and heated for 3 hours to about 180 ⁰ C. The cooled solution is diluted with a further 500 parts by weight of cresol and the solution of 3.5 parts by weight of methyl ethyl ketone oxira and 2 parts by weight of ethanolamine in 6 parts by weight of o-cyclohexylphenol is added.

A copper wire 0.7 mm in diameter is coated with this mixture in the usual V / iron on a wire coating machine in 6 passes. The varnish obtained wire has a good heat-shock resistance, and a softening point of about 300 ⁰ C.

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Claims (6)

Patent claims: 1. Lacquer mixtures, in particular for stoving lacquers, containing Polycondensates containing hydantoin or thiohydantoin rings and solvents and optionally other polymers Fabrics. ". 2. Paint mixture according to claim 1, containing as further polymers Substances ester and / or amide and / or imide groups containing polymers. 3. Paint mixtures according to claim 1, containing hydantoin or thiohydantoin rings containing polycondensates in which the Hydantoin rings via alkylene residues with 4 to 10 carbon atoms, phenylene residues, toluene residues, diphenylenemethane residues or Diphenylätherrrest are linked, solvents as well optionally other polymeric substances. 4. Paint mixtures according to claim 1, containing as a solvent Dialkylamides, N-methylpyrrolidone, dimethyl sulfoxide or cres oil. 5. A process for the production of coatings, characterized in that a hydantoin or Thiohydantoinringe containing polycondensate dissolved in a solvent, applied on a substrate and cured by heating at temperatures between 150 and 500 ⁰ C. 6. coatings consisting of hydantoin or thiohydantoin rings containing polycondensates and optionally other polymeric substances. Le A 9346 - 27 - Documents (Art; / % ι u. - - ■;:. · > «Arden ^ o« ν 4 s is · _ ■.. 90.9841 / U 22